全文获取类型
收费全文 | 255篇 |
免费 | 5篇 |
专业分类
化学 | 172篇 |
晶体学 | 2篇 |
力学 | 6篇 |
数学 | 26篇 |
物理学 | 54篇 |
出版年
2022年 | 1篇 |
2021年 | 2篇 |
2020年 | 3篇 |
2019年 | 5篇 |
2018年 | 5篇 |
2017年 | 2篇 |
2016年 | 4篇 |
2015年 | 9篇 |
2014年 | 4篇 |
2013年 | 12篇 |
2012年 | 14篇 |
2011年 | 12篇 |
2010年 | 16篇 |
2009年 | 7篇 |
2008年 | 21篇 |
2007年 | 13篇 |
2006年 | 15篇 |
2005年 | 10篇 |
2004年 | 7篇 |
2003年 | 15篇 |
2002年 | 8篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1999年 | 6篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 4篇 |
1992年 | 1篇 |
1991年 | 3篇 |
1989年 | 1篇 |
1988年 | 5篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1981年 | 3篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1974年 | 2篇 |
1973年 | 7篇 |
1972年 | 2篇 |
1964年 | 1篇 |
1961年 | 1篇 |
1958年 | 1篇 |
排序方式: 共有260条查询结果,搜索用时 31 毫秒
21.
Yamamoto Y Arakawa T Ogawa R Itoh K 《Journal of the American Chemical Society》2003,125(40):12143-12160
In the presence of a catalytic amount of Cp*RuCl(cod), 1,6-diynes chemoselectively reacted with monoalkynes at ambient temperature to afford the desired bicyclic benzene derivatives in good yields. A wide variety of diynes and monoynes containing functional groups such as ester, ketone, nitrile, amine, alcohol, sulfide, etc. can be used for the present ruthenium catalysis. The most significant advantage of this protocol is that the cycloaddition of unsymmetrical 1,6-diynes with one internal alkyne moiety regioselectively gave rise to meta-substituted products with excellent regioselectivity. Completely intramolecular alkyne cyclotrimerization was also accomplished using triyne substrates to obtain tricyclic aromatic compounds fused with 5-7-membered rings. A ruthenabicycle complex relevant to these cyclotrimerizations was synthesized from Cp*RuCl(cod) and a 1,6-diyne possessing phenyl terminal groups, and its structure was unambiguously determined by X-ray analysis. The intermediary of such a ruthenacycle intermediate was further confirmed by its reaction with acetylene, giving rise to the expected cycloadduct. The density functional study on the cyclotrimerization mechanism elucidated that the cyclotrimerization proceeds via oxidative cyclization, producing a ruthenacycle intermediate and subsequent alkyne insertion initiated by the formal [2 + 2] cycloaddition of the resultant ruthenacycle with an alkyne. 相似文献
22.
Ryuji Tanimoto 《Transformation Groups》2006,11(2):269-294
In this paper we study Freudenburg's counterexample to the fourteenth problem of Hilbert and counterexamples derived from
it. We shall construct a generating set of a nonfinitely generated Ga-invariant ring given in Freudenburg's counterexample by making use of an integral sequence which was constructed inductively
by Freudenburg. This generating set shall be used in describing a generating set of a nonfinitely generated Ga-invariant ring given in Daigle and Freudenburg's counterexample. Using these generating sets, we shall determine the Hilbert
series of the above Freudenburg's and Daigle and Freudenburg's nonfinitely generated Ga-invariant rings, and find that these Hilbert series are rational functions. Then we also show that the Hilbert series of
nonfinitely generated invariant rings appearing in the author's linear counterexamples are rational functions. 相似文献
23.
Yoshihiro Sugi 《中国化学会会志》2010,57(1):1-13
Steric interaction of reagents with zeolites was studied in isopropylation, sec‐butylation, and tert‐butylation of naphthalene (NP) over several large‐pore zeolites to elucidate the mechanism of selective catalysis. Selectivities for dialkylnaphthalene (DAN) isomers were influenced by the type of zeolite and bulkiness of alkylating agent. Selective formation of β,β‐ and 2,6‐diisopropylnaphthalene (DIPN) occurred only over H‐mordenite (MOR) in the isopropylation of NP using propene; bulky transition states of α,α‐ and α,β‐DIPN are excluded because of steric restriction by the channels, resulting in selective formation of β,β‐ and 2,6‐DIPN. However, low selectivities for β,β‐ and 2,6‐DIPN were observed over the zeolites, SSZ‐24 (AFI), SSZ‐55 (ATS), and SSZ‐42 (IFR) with 12‐membered‐ring (12‐MR) pore entrances of one‐dimensional channels, CIT‐5 (CFI), UTD‐1 (DON), and SSZ‐53 (SFH) with 14‐membered‐ring (14‐MR) pore entrances of one‐dimensional channels, and Y‐zeolite (FAU), zeolite β (BEA), and CIT‐1 (CON) with 12‐MR pore entrances of three‐dimensional channels, because their channels are too large for the exclusion of bulky isomers. Catalysis over these zeolites occurs under kinetic and/or thermodynamic control, resulting in predominant formation of α,α‐ and α,β‐DIPN at lower temperatures and an increase of the stable isomer β,β‐DIPN at higher temperatures. The selectivities for β,β‐ and 2,6‐DAN were enhanced with the increase in bulkiness of alkylating agents: 1‐butene for sec‐butylation and 2‐methylpropene for tert‐butylation. In particular, β,β‐di‐tert‐butylnaphthalene (DTBN) was selectively formed in the tert‐butylation. The selectivities for β,β‐ and 2,6‐DAN were enhanced even in large channels: the transition states of the least bulky isomers only fit the channels because other bulky isomers are excluded by steric restriction of the channels. However, tert‐butylation over FAU, BEA, and CON had selectivities for 2,6‐DTBN of around 50–60%, although selectivities for β,β‐DTBN were almost 100% selectivity; these zeolites can hardly recognize the differences between 2,6‐ and 2,7‐DTBN. The results indicate that the fitting of the least bulky isomers to zeolite channels, leading to the exclusion of other bulky isomers, is essential for highly shape‐selective catalysis. 相似文献
24.
A diastereoselective 6π-electrocyclic ring closure employing halogen-substituted 3-amidotrienes via a 1,6-remote asymmetric induction is described. This new asymmetric manifold for pericyclic ring closure further underscores the significance of the allenamide chemistry. 相似文献
25.
N. Bogdanchikova V. Petranovskii Y. Sugi S. Fuentes 《Reaction Kinetics and Catalysis Letters》1999,67(2):371-374
Conditions for stabilization of silver clusters peaking at 320 nm are fond. Role of pH in stabilization of two types of silver
clusters peaking at 320 and 290 nm is discussed. 相似文献
26.
27.
Takahiro Nakae Ryuji Ohnishi Yoshiharu Kitahata Tatsuya Soukawa Hisako Sato Shigeki Mori Tetsuo Okujima Hidemitsu Uno Hiroshi Sakaguchi 《Tetrahedron letters》2012,53(13):1617-1619
6,13-Diiododibenzo[a,h]anthracene and 5,8-diiodopicene were synthesized by AuCl-catalyzed double cyclization. The highly selective reaction yielded a new class of peri-halogenated fused aromatics. 相似文献
28.
29.
Miyagawa T Nagai K Yamada A Sugihara Y Fukuda T Fukuda T Uchida R Tomoda H Omura S Nagamitsu T 《Organic letters》2011,13(5):1158-1161
The first total synthesis of citridone A has been achieved through regioselective intramolecular iodocyclization and regio- and stereoselective Pd(0)-catalyzed coupling as key reactions. 相似文献
30.
Molecular dynamics simulations have been performed to examine the thermodynamic properties of methane/water interface using two different water models, the TIP4P/2005 and SPC/E, and two sets of combining rules. The density profiles, interfacial tensions, surface excesses, surface pressures, and coexisting densities are calculated over a wide range of pressure conditions. The TIP4P/2005 water model was used, with an optimized combining rule between water and methane fit to the solubility, to provide good predictions of interfacial properties. The use of the infinite dilution approximation to calculate the surface excesses from the interfacial tensions is examined comparing the surface pressures obtained by different approaches. It is shown that both the change of methane solubilities in pressure and position of maximum methane density profile at the interface are independent of pressure up to about 2 MPa. We have also calculated the adsorption enthalpies and entropies to describe the temperature dependency of the adsorption. 相似文献